The present invention relates to enol esters of the genus of alkyl side chain methyl substituted or unsubstituted 2,2,6-trimethyl-1-cyclohexen-1-vinyl alkanoates including (but not limited to) beta-cyclohomocitral enol esters, produced by the novel processes of our invention, and novel compositions using one or more of such enol esters to alter, modify or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to consumable materials.
There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product.
"Damascenone-like" (damascenone has the structure: ##STR3## sweet, "cocoa-like", "dried fruit-like", fruity, apple juice-like, sweet carrot juice, incense-like, ionone-like, spicey, woody, wood resin-like, winey, oriental/olibanum, clove-like, camphoraceous, rosey, raspberry, raspberry seed, grape, violet-like, caryophyllene-like, and/or floral aromas with fermented tea and tobacco nuances and sweet vegetable, tea, sweet carrot juice, sweet, fruity, dried fruit-like, apple juice, mimosa, raspberry, pear, ionone-like, "damascenone-like", rosey, woody, camphoraceous, violet, cedarwood-like, caryophyllene-like, wood resin-like, winey, tobacco-like, hay-like, and raspberry kernel tastes (with sweet aftertastes) are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, toothpaste flavors and medicinal product flavors.
Sweet, fruity, acidic-fruity, dried fruit-like, woody, green, beta-ionone-like notes with animal-tobacco topnotes and cognac, balsamic, tobacco undertones are desirable in several types of perfume compositions, perfumed articles and colognes.
Sweet, woody, floral, fruity, ionone-like, spicey, slightly fatty aromatic aromas prior to smoking and sweet, tobacco-like smoke aroma characteristics in the mainstream on smoking are desirable in tobaccos and in tobacco flavoring compositions.
Arctander, "Perfume and Flavor Chemicals", 1969 discloses the use in perfume compositions and flavors of "cyclocitral", "dehydro-beta-cyclocitral", "isocyclocitral", "alpha-cyclocitrylidene acetaldehyde" and "beta-cyclocitrylidene acetaldehyde", thus:
i. "760" CYCLOCITRAL Alpha-cyclocitral = (2,2,6-trimethyl-5-cyclohexen-1-carboxaldehyde). PA1 beta-cyclocitral = (2,2,6-trimethyl-6-cyclohexen-1-carboxaldehyde). Both isomers are known and have been produced separately. ##STR4## Very rarely offered commercially. These particular cyclocitrals have little or no interest to the creative perfumer, but they have served as part of many pieces of proof that isomers (alpha-beta) do often have different odors." PA1 ii. "761: iso-CYCLOCITRAL A mixture of two chemicals: 3,5,6-trimethyl-3-cyclohexen-1-carboxaldehyde (meta-cyclocitral). ##STR5## 2,4,6-trimethyl-4-cyclohexen-1-carboxaldehyde (symmetric-iso-cyclocitral). ##STR6## Powerful, and diffusive, foliage-green, "dark" weedy and dry odor, sometimes described as "Flower-shop odor". The earthy and wet green notes are quite natural in high dilution and resemble the odor of stems from plants and flowers fresh from the soil. PA1 iii. "762: alpha CYCLOCITRYLIDENE ACETALDEHYDE ##STR7## Mild, floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity to the odor of hydrogenated Ionones. Suggested for use in perfume compositions. It brings a certain amount of floral lift to Rose compositions, and performs fairly well even in soap. However, the cost of the rarely offered and never readily available lots are rather discouraging to the perfumer, and it is most conceivable that this material can be left out of the perfumer's library without any great loss. ..." PA1 iv. "763: beta-CYCLOCITRYLIDENE ACETALDEHYDE 2,6,6-trimethyl-1-cyclohexenyl-beta-acrolein. ##STR8## Sweet-woody, rather heavy odor, resembling that of beta-Ionone. More fruity than really floral, but not as tenacious as the Ionone. PA1 v. "869: DEHYDRO-beta-CYCLOCITRAL (Safranal) 2,6,6-trimethyl-4,4-cyclohexadiene-1-carboxaldehyde ##STR9## Very powerful, sweet, green-floral and somewhat tobacco-herbaceous odor of good tenacity. In extreme dilution reminiscent of the odor of Safran (Saffron).
Finds use in perfume compositions where it blends excellently with Oakmoss products (compensates for sweetness and lifts the topnote), with Ionones (freshness), Geranium and Galbanum (enhances the green and "vegetable" notes), etc. ..."
Suggested for use in perfume compositions, but since it does not offer any new or unusual odor characteristics, and it cannot be produced in economical competition to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer. ..."
Interesting material for fresh topnotes, as a modifier for aldehydic-citrusy notes, as a green-floral topnote in flower fragrances, etc. It blends excellently with the aliphatic Aldehydes, with Oakmoss products and herbaceous oils. ..."
Safranal and beta-cyclocitral are disclosed as volatile constituents of Greek Tobacco by Kimland et al., Phytochemistry 11 (309) 1972. Beta-cyclocitral is disclosed as a component of Burley Tobacco flavor by Demole and Berthet, Helv. Chim. Acta. 55 Fasc 6, 1866 (1972).
Methods for producing enol esters are disclosed in the prior art. Thus, for example, heptaldehyde enol acetate is disclosed to be produced according to the process of reacting heptaldehyde with acetic anhydride in the presence of crystalline potassium acetate at reflux temperatures of 155.degree.-160.degree. C. by Bedoukian, J. Am. Chem. Soc. 66, August, 1944, pages 1325-1327.
However, no disclosures exist in the prior art indicating the existence or implying the organoleptic uses of enol esters related to those of the instant invention or methods for synthesizing such compounds.